CN1441827A - Mixtures of phosphorus-containing compounds used as polymer stabilizers - Google Patents

Mixtures of phosphorus-containing compounds used as polymer stabilizers Download PDF

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CN1441827A
CN1441827A CN01812710.XA CN01812710A CN1441827A CN 1441827 A CN1441827 A CN 1441827A CN 01812710 A CN01812710 A CN 01812710A CN 1441827 A CN1441827 A CN 1441827A
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suitably
straight
branched
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cycloalkyl
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CN1217983C (en
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P·施塔尼克
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Clariant Finance BVI Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
    • C09K15/324—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus containing phosphorus and sulfur

Abstract

The invention relates to a synergistic mixture comprising a) at least one compound selected from the group consisting of the phosphites of the formula (I) to (V), of the phosphonites of the formulae (VI) to (IX) and (XV), of the di/oligophosphonites of the formulae (X) and (XI) and of the phosphinites of the formulae (XII) to (XIV), and b) at least one compound selected from the group consisting of the phosphanes of the formula (XVI), the diloligophosphanes of the formulae (XVII) and (XVIII), and of the cyclophosphanes of the formula (XIX), and also to a process for stabilizing polymers with respect to thermooxidative degradation by addition and incorporation of a synergistic mixture of this type.

Description

Be used as the mixture of the P contained compound of polymer stabilizer
The present invention relates to mixture, it comprises phosphorous acid ester, phosphinate, phosphinate, especially aromatic series phosphinate or phosphorous acid ester (component 1) and tertiary phosphine alkane (component 2) and relates to mixture by using the type in the method for stabilization of polymer aspect heat or the mechanical stress risers degraded.
Be surprisingly found out that it is more effective that the compound that comprises component 1 is used for polymkeric substance as stablizer together with the mixture of the compound of component 2 separately than corresponding component.
As well known by persons skilled in the art, phosphorous acid ester, phosphinate and/or phosphinate are used to during processing stabilization of polymer aspect thermooxidative degradation.In this connection, the triphenylphosphine of use alkane (triphenylphosphine has been arranged; TPP) description.The stabilization of this class material shows, stable polymer has unaltered in fact melt viscosity (this is the yardstick of molecular weight stability) and color characteristics preferably like this, promptly, has lower painted level after extruding with unstabilized polymer phase ratio.
If use the mixture of two or more additives, be contemplated that performance will change linearly as the function of its blending ratio.
Yet have been found that for two kinds of components 1 of above-mentioned definition and 2 mixture aspect melt flow stabilization and/or colour stableization, compare with the linear change of expecting between the value of independent component, there is favourable skew in linear relationship.This behavior is known as synergetic property.
According to the present invention, a kind of mixture is provided, it comprises as the component 1 of structure branch (a) with as the component 2 of structure branch (b).
Component 1 is made up of to the compound of (XV) one or more general formulas (I):
Figure A0181271000111
Figure A0181271000112
Figure A0181271000113
Figure A0181271000114
Figure A0181271000115
Figure A0181271000121
Figure A0181271000122
Figure A0181271000125
Figure A0181271000132
Component 2 is made up of to the compound of (XIX) one or more general formulas (XVI):
Figure A0181271000135
Figure A0181271000141
Figure A0181271000142
Wherein, independently of each other,
R 1Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 2Be H, C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 3Be the group of n-valency, its type is C 1-C 30-alkylidene group (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 1-C 30-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 12-cycloalkylidene or C 6-C 24-arylidene is (if suitably by C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18Alkoxyl group replaces);
R 4Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 5Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 6Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
A is direct keyed jointing, C 1-C 30-alkylidene (if suitably also comprising heteroatoms N, O, P, S),＞NH,＞NR 1,-S-,＞S (O),＞S (O) 2,-O-;
D is the group of q-valency, and its type is C 1-C 30-alkylidene group (straight chain, side chain is if suitably also comprise heteroatoms N, O, P, S), C 1-C 30-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 12-cycloalkylidene (if suitably also comprising heteroatoms N, O, P, S) or C 6-C 24-arylidene is (if suitably also by C 1-C 18-alkyl (straight or branched), C 5-C 12Cycloalkyl or C 1-C 18Alkoxyl group replaces) ,-O-,-S-;
X is Cl, Br, F, OH (tautomeric form＞P (O) H that comprises generation);
K is 0 to 4;
N is 1 to 4;
M is 0 to 5;
P is 0 or 1;
Q is 1 to 5;
R is 3 to 6, the group P-R in its formula of (XIX) 6Be the structure branch of phosphorus heterocycle, represent by the * on the key that even goes out from P.
In the preferred compound, group
R 1' be C 6-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 2-C 24-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12Alkoxyl group replaces);
R 2' be H, C 1-C 12-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 18-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 3' be the group of n-valency, its type is C 1-C 14-alkylidene group (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 1-C 18-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 8-cycloalkylidene or C 6-C 24-arylidene is (if suitably by C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 4' be C 1-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 24-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 5' be C 8-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 18-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 6' be C 5-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 18-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
A ' is direct keyed jointing, C 1-C 18-alkylidene (if suitably also comprising heteroatoms N, O, P, S),＞NH ,-S-,-O-;
D ' is the group of q '-valency, and its type is C 1-C 24-alkylidene group (straight chain, side chain is if suitably also comprise heteroatoms N, O, P, S), C 1-C 24-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 8-cycloalkylidene (if suitably also comprising heteroatoms N, O, P, S) or C 6-C 24-arylidene is (if suitably also by C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
X ' is F or OH (tautomeric form＞P (O) H that comprises generation);
K ' is 0 to 3;
N ' is 1 to 4;
M ' is 0 to 3;
P ' is 0 or 1;
Q ' is 1 to 4;
R ' is 4 or 5, the group P-R in its formula of (XIX) 6Be the structure branch of phosphorus heterocycle, represent by the * on the key that even goes out from P.
In the especially preferred compound, group
R 1" be C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 2" be C 1-C 8-alkyl (straight or branched), C 5-C 8-cycloalkyl, C 1-C 18-alkylaryl, C 6-C 12-aryl or heteroaryl, C 6-C 12-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 3" be the group of n-valency, its type is C 1-C 12-alkylidene group (straight or branched is if suitably also comprise heteroatoms N or P), C 1-C 12-alkylidene (if suitably also comprising heteroatoms N or P), C 6-C 8-cycloalkylidene or C 6-C 12Arylidene is (if suitably also by C 1-C 12-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 4" be C 1-C 8-alkyl (straight or branched), C 5-C 8-cycloalkyl, C 1-C 18-alkylaryl, C 6-C 12-aryl or heteroaryl, C 6-C 12-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 5" be C 12-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 6-C 8-cycloalkyl, C 1-C 12-alkylaryl, C 6-C 18-aryl or heteroaryl, C 6-C 18-aryl or heteroaryl are (by group C 1-C 8-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 6" be C 5-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl, C 1-C 12-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
A " be direct keyed jointing, C 1-C 18-alkylidene (if suitably also comprising heteroatoms N, O, P, S),＞NH ,-S-,-O-;
D " be q "-group of valency, its type is C 1-C 24-alkylidene group (straight chain, side chain is if suitably also comprise heteroatoms N, O, P, S), C 1-C 24-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 8-cycloalkylidene (if suitably also comprising heteroatoms N, O, P, S) or C 6-C 24-arylidene is (if suitably also by C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
X " be F or OH (tautomeric form＞P (O) H that comprises generation);
K " be 0 to 3;
N " be 1 to 4;
M " be 0 to 3;
P " be 0 or 1;
Q " be 1 to 4;
R " be 4 or 5, the group P-R in its formula of (XIX) 6Be the structure branch of phosphorus heterocycle, represent by the * on the key that even goes out from P.
Particularly suitable mixture be all pass through to form in conjunction with following specified component 1 and 2 those:
Component 1
-compound, its main ingredient are four (two-tert-butyl-phenyl) xenyl-two phosphinates
-three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester
-two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites
-two (2,4-(1, the 1-dixylyl) phenyl) tetramethylolmethane base diphosphites
-two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane base diphosphites
-two (octadecyl) tetramethylolmethane base diphosphites
-three (nonyl phenyl) phosphorous acid ester
-2,2 ', 2 "-nitrilo triethyl three (3,3 '-5,5 '-tetra-tert-1,1 '-phenylbenzene-2,2 '-two basic phosphorous acid esters)
-two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester
-2-(2,4, the 6-tri-butyl-phenoxy)-5-butyl-5-ethyl-1,3, oneself encircles (dioxaphosphorinane) 2-two oxa-phosphas
-methylene radical-2,2 '-two (4, the 6-di-tert-butyl-phenyl) 2-ethylhexyl phosphorous acid ester
-1,1-ethidine-2,2 '-two (4, the 6-di-tert-butyl-phenyl) fluorophosphite
Component 2
-triphenylphosphine alkane
-three (2 aminomethyl phenyl) phosphine alkane
-three (4 aminomethyl phenyl) phosphine alkane
-three (2 p-methoxy-phenyl) phosphine alkane
-three (4 p-methoxy-phenyl) phosphine alkane
-Fourth Ring hexyl ring tetraphosphine alkane
-tetra-tert ring tetraphosphine alkane
-quaterphenyl basic ring tetraphosphine alkane
-tetraphenyl ring tetraphosphine alkane
-pentaphene basic ring five phosphine alkane
-tetraphenyl diphosphine
-Fourth Ring hexyl diphosphine
-two (diphenylphosphino) methane
-1, two (diphenylphosphino) ethane of 2-
-1, two (diphenylphosphino) propane of 3-
-1, two (diphenylphosphino) butane of 4-
-1, two (diphenylphosphino) pentanes of 5-
-1, two (diphenylphosphino) hexanes of 6-
-1, two (diphenylphosphino) octanes of 8-
-1, two (diphenylphosphino)-2 of 3-, 2-dimethylpropane
-1,1,1-three (diphenylphosphine ylmethyl) methane
-1,1,1-three (diphenylphosphine ylmethyl) ethane
-1,1,1-three (diphenylphosphine ylmethyl) propane
-1,1,1-three (diphenylphosphine ylmethyl) butane
-1,1,1-three (diphenylphosphine ylmethyl)-1-phenylmethane
-1, two (diphenylphosphine the ylmethyl)-2-diphenylphosphino propane of 3-
-1, two (the diphenylphosphino)-2-methylpropanes of 3-
In these mixtures, especially preferred following component 1 and 2 mixture
A) wherein component 1 is that three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and component 2 are triphenylphosphines;
B) wherein component 1 is that two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites and component 2 are triphenylphosphine alkane;
C) wherein component 1 is by four (di-tert-butyl-phenyl) xenyl, two phosphinates, two (2, the 4-di-tert-butyl-phenyl) mixture (being called PS-1 hereinafter) and the component 2 of phenylbenzene list phosphinate and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester composition are triphenylphosphine alkane;
D) wherein component 1 is that three (nonyl phenyl) phosphorous acid esters and component 2 are triphenylphosphine alkane
E) wherein component 1 is 2-(2,4, the 6-tri-butyl-phenoxy)-5-butyl-5-ethyl-1,3, and own ring of 2-two oxa-phosphas and component 2 are triphenylphosphine alkane;
F) wherein component 1 is that three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and component 2 are 1, two (diphenylphosphino)-2 of 3-, 2-dimethylpropane;
G) wherein component 1 is that two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites and component 2 are 1, two (diphenylphosphino)-2 of 3-, 2-dimethylpropane;
H) wherein component 1 comprises that the compound of mixture PS-1 and component 2 are 1, two (diphenylphosphino)-2 of 3-, 2-dimethylpropane;
I) wherein component 1 is that three (nonyl phenyl) phosphorous acid esters and component 2 are 1, two (diphenylphosphino)-2 of 3-, 2-dimethylpropane;
J) wherein component 1 is 2-(2,4, the 6-tri-butyl-phenoxy)-5-butyl-5-ethyl-1,3, and own ring of 2-two oxa-phosphas and component 2 are 1, two (diphenylphosphino)-2 of 3-, 2-dimethyl-propane;
K) wherein component 1 is that three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) ethane;
L) wherein component 1 is that two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) ethane;
M) wherein component 1 comprises that the compound of mixture PS-1 and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) ethane;
N) wherein component 1 is that three (nonyl phenyl) phosphorous acid esters and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) ethane;
O) wherein component 1 is 2-(2,4, the 6-tri-butyl-phenoxy)-5-butyl-5-ethyl-1,3, and own ring of 2-two oxa-phosphas and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) ethane;
P) wherein component 1 is that three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) propane;
Q) wherein component 1 is that two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) propane;
R) wherein component 1 comprises that the compound of mixture PS-1 and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) propane;
S) wherein component 1 is that three (nonyl phenyl) phosphorous acid esters and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) propane;
T) wherein component 1 is 2-(2,4, the 6-tri-butyl-phenoxy)-5-butyl-5-ethyl-1,3, and own ring of 2-two oxa-phosphas and component 2 are 1,1,1-three (diphenylphosphine ylmethyl) propane.
The amount that component 1 exists in mixture of the present invention is that 1 to 99 weight % and component 2 are 99 to 1 weight %.
Component 1 preferred amount is that 5 to 95 weight %, preferred especially 10 to 90 weight % and component 2 preferred amounts are 95 to 5 weight %, preferred especially 90 to 10 weight %.
The working concentration of mixture of the present invention changes with the character of polymkeric substance.For any given situation, those skilled in the art can easily determine this amount, are 0.001 to 5 weight %, preferred 0.005 to 3 weight %, preferred especially 0.01 to 2 weight % but be based on the general amount of polymer materials that is stabilized.
The mixture that constitutes by component 1 and 2 can by simple mixing, by sneak into melt, by with a kind of components dissolved or be dispersed in liquid or other components of fusing in, by mixing two kinds of melts or by common fusing, in each case, then carrying out cooling step if desired prepares.Also the solution in being fit to solvent prepares mixture of the present invention by mixing and concentrated component.The preparation of mixture can be the intermittent process in for example various mixing machines of equipment that are fit to or reactor or the like, also can be the successive processes in forcing machine or continuous mixer or kneading machine or roller refining machine for example.If desired, can use compacting, granulation, suppress, extrude or business form that other method produce to be fit to.
The present invention also is provided at the method for thermooxidative degradation aspect stabilisation of polymeric materials.This method comprises, before the polymerization stage, during or (usually) afterwards, add and in conjunction with the mixture of the present invention of stable quantity, it can be solid or fusion form, can be in solution (preferably as liquid concentrate) or as solid masterbatch (if being suitable for), consumption makes stabilizer concentration reach 0.001 to 5 weight %, preferred 0.005 to 3 weight %, preferred especially 0.01 to 2 weight %, based on the polymkeric substance that is stabilized.
The liquid concentrate of the type comprises the mixture of the present invention of 10 to 80 weight % and the solvent of 90 to 20 weight %.
The masterbatch of the type (being also referred to as the solid-based mixing material) comprises the polymer materials of the mixture of the present invention of 10 to 80 weight %, preferred 40 to 70 weight %, preferred especially 15 to 40 weight % and 90 to 20 weight %, preferred 60 to 30 weight %, preferred especially 85 to 60 weight %, and this polymer materials is identical with the polymer materials that is stabilized or compatible.
The all components of mixture of the present invention can use known method preparation from compound known.The summary for preparing the reaction process of component 1 and 2 is found in for example G.M.Kosolapoff, Organic Phosphorus Compounds, volume 1-7, Wiley Verlag, New York, 1972, perhaps Houben/Weyl, Methoden der Organischen Chemie[organic chemistry method], roll up 12, the 4 editions, Georg Thieme Verlag, Stuttgart, 1963 and sequel accordingly.Use this information, those skilled in the art can prepare above-claimed cpd.The content of these references is hereby incorporated by.
The compound of the compound of general formula (XVIII) and general formula (XIX) also by the following method the preparation: make general formula R ' 1R ' 1The secondary phosphine alkane of PH or general formula R ' 1PH 2Uncle phosphine alkane and halogen, preferred chlorine or bromine reaction, if if suitable at acid scavenger, for example oxide compound, oxyhydroxide or basic metal or alkaline-earth metal carbonate or amine, preferred tertiary amine in the presence of and suitably in the presence of inert solvent.Secondary phosphine alkane provides the compound of general formula (XVIII).Uncle's phosphine alkane provides the compound of general formula (XIX).In the method, advantageously use alkylphosphines alkane material to start with, these obtain on a large scale than the halophosphines alkane that is used for prior art is easier.The example that this method describes in detail is shown in FR 2739381 or GB 2306478.
Selectively and normally, this compounds preparation is from organic halogenide, for example alkyl or aryl chloride or alkyl or aryl bromide, and PCl 3, the Wurtz reaction that wherein utilizes the Grignard reaction or change; Perhaps react by means of Friedel-Crafts; Perhaps by containing the addition reaction of P-H compound on multiple bond, perhaps react, succeeded by reduction, perhaps by means of the derivatization reaction of preformed phosphine alkane by the Arbuzov of organic diphosphinic acid ester with Organohalogen compounds.
The mixture that the present invention is made by component 1 and 2 can be preferred for as the processing stabilizers of polymer materials
1. the polymkeric substance of monoolefine and diolefine, for example polypropylene, polyisobutene, polybutene-1, poly 4-methylpene-1, polyisoprene or polyhutadiene, and the cycloolefin polymkeric substance of cyclopentenes or norbornylene for example, polyethylene (randomly can be crosslinked), for example high density polyethylene(HDPE) (PE-HD), new LDPE (film grade) (PE-LD), linear low density polyethylene (PE-LLD), branched low density polyethylene (PE-BLD).Polyolefine, i.e. monoolefine polymer, especially polyethylene and polypropylene, can be by different and preparation especially by the following method:
A) radical polymerization (usually under high pressure and high temperature).
B) catalyzed polymerization uses the catalyzer that usually comprises the metal of the IVb of family, Vb, VIb or VIII in one or more periodictables.These metals have one or more ligands usually, are typically oxide compound, halogenide, alcoholate, ester, ether, amine, alkyl, alkenyl and/or aryl, and it both can be that π-coordination also can be σ-coordination.These metal complexess can be free form or be fixed on the carrier, usually be fixed on activation magnesium chloride, titanium chloride, aluminum oxide or the silicon oxide.These catalyzer can be soluble or undissolved in polymerisation medium.Described catalyzer can use separately in polymerization, perhaps can use other activators, be typically metal alkyls, alkyl metal halide, alkyl metal oxide, for example or metal alkyloxanes, described metal is the element of the Ia of family, IIa and/or IIIa in the periodictable.Described activator can be easily with other esters, ether, amine or silyl ether groups.The so-called Phillips of these catalyst systems, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), metallocene or single-site catalysts (SSC).
2. 1) in the mixture of polymers mentioned, for example mixture of polypropylene and polyisobutene, polypropylene and polyethylene (PP/HDPE for example, mixture PP/LDPE) and dissimilar poly mixtures (for example LDPE/HDPE).
Monoolefine and diolefine mutual or with the multipolymer of other vinyl monomer, ethylene-propylene copolymer for example, LLDPE (PE-LLD) and with the mixture of new LDPE (film grade) (PE-LD), propene-1-butene-1 multipolymer, propylene-isobutylene copolymers, ethene-1-Butylene copolymer, ethene-hexene copolymer, ethene-methylpentene multipolymer, ethene-heptene multipolymer, ethylene-octene copolymer, propylene-butadienecopolymer, isobutylene-isoprene copolymer, ethylene-acrylic acid alkyl ester copolymer, the ethylene-methyl methacrylate alkyl ester copolymer, the multipolymer of vinyl-vinyl acetate copolymer and itself and carbon monoxide or ethylene-acrylic acid copolymer and its salt (ionomer) and ethene and propylene and diolefine be hexadiene for example, the terpolymer of Dicyclopentadiene (DCPD) or ethidine-norbornylene; With this analog copolymer each other mixture and with above-mentioned 1) in the mixture of polymers mentioned, polypropylene-ethylene-propylene copolymer for example, the PE-LD-ethylene-vinyl acetate copolymer, the PE-LD-ethylene-acrylic acid copolymer, the PE-LLD-ethylene-vinyl acetate copolymer, the PE-LLD-ethylene-acrylic acid copolymer and alternately or random polyalkylene-carbon monoxide multipolymer and with other polymkeric substance mixture of polymeric amide for example.
4. hydrocarbon resin (C for example 5-C 9), comprise the mixture of its hydrogenation modified product (for example tackifier) and polyalkylene and starch.
5. polystyrene gathers (p-methylstyrene), poly-(alpha-methyl styrene).
6. the multipolymer of vinylbenzene or alpha-methyl styrene and diolefine or acrylate derivative, for example styrene butadiene, styrene-acrylonitrile, vinylbenzene-alkyl methacrylate, styrene butadiene-alkyl acrylate, styrene butadiene-alkyl methacrylate, phenylethylene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; High impact strength of styrene multipolymer and other polymkeric substance be the mixture of polyacrylic ester, diene polymer or ethylene-propylene-diolefine ter-polymers for example; With cinnamic segmented copolymer, for example styrene-butadiene-styrene, styrene-isoprene-phenylethene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.
7. the graft copolymer of vinylbenzene or alpha-methyl styrene, for example vinylbenzene grafting on polyhutadiene, vinylbenzene is in grafting on the Polybutadiene-styrene or grafting on polybutadiene-acrylonitrile copolymer; Vinylbenzene and vinyl cyanide (perhaps methacrylonitrile) grafting on polyhutadiene; The grafting on polyhutadiene of vinylbenzene, vinyl cyanide and methyl methacrylate; The grafting on polyhutadiene of vinylbenzene and maleic anhydride; The grafting on polyhutadiene of vinylbenzene, vinyl cyanide and maleic anhydride or maleimide; The grafting on polyhutadiene of vinylbenzene and maleimide; The grafting on polyhutadiene of vinylbenzene and alkyl acrylate or alkyl methacrylate; The grafting on ethylene-propylene-diene terpolymers of vinylbenzene and vinyl cyanide; Vinylbenzene and vinyl cyanide on polyalkyl acrylate or polyalkyl methacrylate, vinylbenzene and vinyl cyanide grafting on acrylate-butadienecopolymer, with and with 6) in the mixture of the multipolymer listed, be called as the copolymer mixture of ABS, MBS, ASA or AES polymkeric substance.
8. polymer containing halogen, for example sovprene, chlorinated rubber, chlorination or sulphur chlorinatedpolyethylene, the multipolymer of ethene and chloro ethene, Epicholorohydrin homopolymer and multipolymer, the polymkeric substance of especially halogen-containing vinyl compound, for example polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride) with and multipolymer, for example vinylchlorid-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate copolymer.
9. derived from alpha, the polymkeric substance of beta-unsaturated acid and derivative thereof, for example polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and polyacrylonitrile, it carries out impact modified with butyl acrylate.
10. 9) in the monomer mentioned mutually or with the multipolymer of other unsaturated monomer, for example multipolymer or the vinyl cyanide-alkyl methacrylate-butadiene terpolymer of acrylonitrile butadiene copolymer, vinyl cyanide-alkyl acrylate copolymer, vinyl cyanide-alkoxyalkyl acrylate or vinyl cyanide-vinyl halide.
11. derived from the polymkeric substance of unsaturated alkohol and amine or its acyl derivative or acetal, for example polyvinyl alcohol, polyvinyl acetate (PVA), polyvinyl stearate, polyphenyl formic acid vinyl ester, polyvinyl maleic acid ester, polyvinyl butyral acetal, polyene propyl group phthalic ester or polyene propyl group melamine; With and with above-mentioned 1 in the multipolymer of the alkene mentioned.
12. the homopolymer of cyclic ethers and multipolymer, for example multipolymer of polyglycol, polyoxyethylene, polyoxytrimethylene or itself and bisglycidyl base ether.
13. polyacetal, for example polyoxymethylene comprises the polyoxymethylene of oxyethane as comonomer with those; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.
14. the mixture of polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide.
15. derived from the one hand be polyethers, polyester or the polyhutadiene of hydroxy terminal and be the urethane of aliphatics or aromatic poly-isocyanate on the other hand, with and precursor.
16. polymeric amide and copolyamide, it is derived from diamines and dicarboxylic acid and/or aminocarboxylic acid or corresponding lactam, for example polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12, the aromatic poly that begins from m-xylene diamine and hexanodioic acid; With hexanediamine and m-phthalic acid or terephthalic acid and the polymeric amide that has or do not have elastomerics to prepare, for example gather 2,4,4-tri-methyl hexamethylene terephthaloyl diamines or poly-metaphenylene isophthaloyl diamines as properties-correcting agent; And above-mentioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemically keyed jointing or the elastomeric segmented copolymer of grafted; Perhaps with polyethers for example with the segmented copolymer of polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; And with the polymeric amide or the copolyamide of EPDM or ABS modification; Polymeric amide (RIM polymeric amide system) with the work in-process condensation.
17. polyureas, polyimide, polyamide-imide and polybenzimidazole.
18. polyester derived from dicarboxylic acid and glycol and/or hydroxycarboxylic acid or corresponding lactone, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-hydroxymethyl-cyclohexane terephthalate, polyalkylene naphthalates and poly-hydroxybenzoate, and derived from the block copolyether ester of the polyethers of hydroxy terminal; And with the polyester of polycarbonate or MBS modification.
19. polycarbonate and polyestercarbonate.
20. polysulfones, polyethersulfone and polyetherketone.
21. derived from being aldehyde on the one hand and being the cross-linked polymer of phenol, urea and melamine, for example phenol/formaldehyde resins, urea/formaldehyde resin and melamine/formaldehyde resin on the other hand.
22. the Synolac of dryness and non-dryness.
23. derived from saturated and unsaturated dicarboxylic acid and polyvalent alcohol with as the unsaturated polyester resin of the copolyesters of the vinyl compound of linking agent, with and have a halogen-containing modifier of low combustible.
24. derived from the crosslinkable acrylic resin of the acrylate that replaces, for example epoxy acrylate, urethane acrylate or polyester acrylate.
25. Synolac, vibrin and acrylic resin with melamine resin, urea resin, polymeric polyisocyanate or cross linking of epoxy resin.
26. derived from the cross-linked epoxy resin of polyepoxide, derived from diglycidylether or alicyclic diepoxide.
27. natural polymkeric substance, for example Mierocrystalline cellulose, rubber, gelatin and its be with the polymkeric substance homogeneous phase mode corresponding derivative of modification chemically, for example cellulose acetate, cellulose propionate and cellulose butyrate or ether of cellulose methylcellulose gum for example; And rosin and its derivative.
28. above-mentioned blend polymer, PP/EPDM for example, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrylate, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/PE-HD, PA/PP, PA/PPO.
29. exist naturally and the synthetic organic materials, it is the compound of pure monomer or the mixture of this compounds, for example mineral oil, animal and plant fat, oil and wax, perhaps based on oil, fat and the wax of the mixture of synthetic ester (for example phthalic ester, adipic acid ester, phosphoric acid ester or trimellitate) and synthetic ester, the mineral oil that wherein has any weight ratio, usually as those of spinning component, and the water miscible liquid of this class material.
30. natural or elastomeric water miscible liquid, for example natural rubber latex or carboxyl styrene/butadiene copolymer latices.
Other additives may reside in these polymkeric substance, for example oxidation inhibitor, photostabilizer (UV absorption agent and/or HALS compound), metal passivator, peroxide degradation agent, polymeric amide stablizer, alkaline auxiliary stabilizer, nucleator, filler, toughener, softening agent, lubricant, emulsifying agent, pigment and dyestuff, optical brightener, fire retardant, static inhibitor, whipping agent or the like.
These other additives can be before mixture of the present invention adds, simultaneously or join polymkeric substance afterwards.As mixture of the present invention, these additives can solid, solution or melt-stoichiometry, perhaps with solid or liquid mixture or masterbatch or the metering of concentrate form, both can also can measure continuously in batches.
The present invention also comprises the product that obtains through the processing that is shaped from above-mentioned polymkeric substance, and this polymkeric substance comprises mixture of the present invention and at least a other additive of mentioning.
By the advantageous effect of following examples explanation according to the mixture of the present invention's preparation.
Embodiment 1
Prepare mixture of the present invention from three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (component 1) and triphenylphosphine alkane (component 2):
In 250ml flask, at rare gas element (N with agitator (having the precision glass seal cartridge) 2) under, with pulverous mixture of three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (component 1) and triphenylphosphine alkane (component 2), with every kind of following blending ratio, fusion under agitation and homogenizing under 190 ℃ of temperature.The mixture melt that obtains is poured in the porcelain dish, and it cools off post-hardening.Every batch scale is 100g.
Table 1
Component 1 and 2 amount in the mixture of the present invention (1)
Mixture Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester [weight %] Triphenylphosphine alkane [weight %]
????1a ????100 ????0
????1b ????70 ????30
????1c ????50 ????50
????1d ????30 ????70
????1e ????0 ????100
Embodiment 2
Prepare mixture of the present invention from two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites (component 1) and triphenylphosphine alkane (component 2):
In 250ml flask, at rare gas element (N with agitator (having the precision glass seal cartridge) 2) under, with pulverous mixture of two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites (component 1) and triphenylphosphine alkane (component 2), with every kind of following blending ratio, fusion under agitation and homogenizing under 190 ℃ of temperature.The mixture melt that obtains is poured in the porcelain dish, and it cools off post-hardening.Every batch scale is 100g.
Table 2
Component 1 and 2 amount in the mixture of the present invention (2)
Mixture Two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane base diphosphites [weight %] Triphenylphosphine alkane [weight %]
????2a ????100 ????0
????2b ????70 ????30
????2c ????50 ????50
????2d ????30 ????70
????2e ????0 ????100
Embodiment 3
Prepare mixture of the present invention from four (2, the 4-di-tert-butyl-phenyl) xenyl-two phosphinates (main ingredient among the Sandostab P-EPQ, use, CLARIANT AG) (component 1) and triphenylphosphine alkane (component 2):
In 250ml flask, at rare gas element (N with agitator (having the precision glass seal cartridge) 2) under, with pulverous mixture of Sandostab P-EPQ (component 1) and triphenylphosphine alkane (component 2), with every kind of following blending ratio, fusion under agitation and homogenizing under 190 ℃ of temperature.The mixture melt that obtains is poured in the porcelain dish, and it cools off post-hardening.Every batch scale is 100g.
Table 3
Component 1 and 3 amount in the mixture of the present invention (3)
Mixture Sandostab P-EPQ [weight %] Triphenylphosphine alkane [weight %]
????3a ????100 ????0
????3b ????70 ????30
????3c ????50 ????50
????3d ????30 ????70
????3e ????0 ????100
Embodiment 4
In order to prepare according to stable polymer of the present invention (4a), will
100 parts polypropylene (eltex P HL 001PF, Solvay)
0.05 the Irganox 1010 of part
0.10 part calcium stearate and
0.04 the mixture of the present invention (1a) of part
It is a powder type, mixes in mixing machine, makes its homogenizing, the polymer-extruded thing pelletizing that will obtain then by extruding then under mild conditions in single screw extrusion machine (Collin, 210 ℃, 80/min, compr.1: 3, die head 4mm).Prepare stable polymer (4b) to (4e) from mixture (1b) to (1e) similarly.
In order to study melt flow stabilization and colour stableization, these stable polymer (4a) are carried out extruding for 5-time in 270 ℃ in single screw extrusion machine (G ttfert Extrusiometer, 50/min, compr.1: 3, die head 2mm) to (4e).According to ASTM 1238, condition L (230 ℃/2.16kg) melt flow index (MFI) and according to the yellowness index (YI) of DIN 6167 the 5th time by after mensuration.What obtain the results are shown in following table.
Table 4
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (1a) to the PP of (1e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????4a ????0 ????13.48 ????10.8
????4b ????30 ????9.99 ????9.6
????4c ????50 ????6.49 ????10.4
????4d ????70 ????4.63 ????10.3
????4e ????100 ????4.80 ????11.8
Embodiment 5
Prepare stable polymer (5a) to (5e) in the mode that is similar among the embodiment 4 from mixture (1a) to (1e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 5
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (1a) to the PP of (1e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????5a ????0 ????10.85 ????12.8
????5b ????30 ????5.60 ????10.2
????5c ????50 ????4.51 ????10.2
????5d ????70 ????4.43 ????8.6
????5e ????100 ????4.24 ????8.3
Embodiment 6
Prepare stable polymer (6a) to (6e) in the mode that is similar among the embodiment 4 from mixture (2a) to (2e), concentration is 0.04 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 6
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (2a) to the PP of (2e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
???MFI[g/10min] ????YI
????6a ????0 ????5.34 ????8.5
????6b ????30 ????4.55 ????5.3
????6c ????50 ????4.19 ????5.5
????6d ????70 ????4.75 ????9.9
????6e ????100 ????4.80 ????11.8
Embodiment 7
Prepare stable polymer (7a) to (7e) in the mode that is similar among the embodiment 4 from mixture (2a) to (2e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 7
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (2a) to the PP of (2e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
??MFI[g/10min] ?????YI
????7a ????0 ????4.27 ????6.2
????7b ????30 ????4.09 ????4.3
????7c ????50 ????3.58 ????4.5
????7d ????70 ????3.78 ????5.5
????7e ????100 ????4.24 ????8.3
Embodiment 8
Prepare stable polymer (8a) to (8e) in the mode that is similar among the embodiment 4 from mixture (3a) to (3e), concentration is 0.04 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 8
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (3a) to the PP of (3e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
????MFI[g/10min] ????YI
????8a ????0 ????8.28 ????8.0
????8b ????30 ????6.30 ????8.4
????8c ????50 ????5.11 ????7.9
????8d ????70 ????4.70 ????9.4
????8e ????100 ????4.80 ????11.8
Embodiment 9
Prepare stable polymer (9a) to (9e) in the mode that is similar among the embodiment 4 from mixture (3a) to (3e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 9
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (3a) to the PP of (3e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????9a ????0 ????5.23 ????7.5
????9b ????30 ????4.43 ????5.9
????9c ????50 ????4.04 ????5.8
????9d ????70 ????4.21 ????6.5
????9e ????100 ????4.24 ????8.3
Clearly illustrate as the result of embodiment (4) to (9), all these mixtures of the present invention (1) have obvious synergistic to (3) with used as stabilizers, (MFI and YI are respectively to concentration of component in the mixture) more can illustrate this point if the result is presented in diagrammatic form.In all cases, measure the straight line of the curve of performance (MFI value or YI value) well below the independent component of connection of theory anticipation, promptly the performance of mixture is more much better than what expect.
Embodiment 10
From three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (component 1) and two (diphenylphosphino)-2,2-dimethylpropane (component 2) prepares mixture of the present invention:
In 250ml flask, at rare gas element (N with agitator (having the precision glass seal cartridge) 2) under, with three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (component 1) and two (diphenylphosphino)-2, pulverous mixture of 2-dimethylpropane (component 2), with every kind of following blending ratio, fusion under agitation and homogenizing under 190 ℃ of temperature.The mixture melt that obtains is poured in the porcelain dish, and it cools off post-hardening.Every batch scale is 50g.
Table 10
Component 1 and 2 amount in the mixture of the present invention (10)
Mixture Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester [weight %] Two (diphenylphosphino)-2,2-dimethylpropane [weight %]
????10a ????100 ????0
????10b ????70 ????30
????10c ????50 ????50
????10d ????30 ????70
????10e ????0 ????100
Embodiment 11
From three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (component 1) and 1,1,1-three (diphenylphosphine ylmethyl) propane (component 2) prepares mixture of the present invention:
In 250ml flask, at rare gas element (N with agitator (having the precision glass seal cartridge) 2) under, with three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (component 1) and 1,1, pulverous mixture of the basic propane of 1-three (diphenylphosphine ylmethyl) (component 2), with every kind of following blending ratio, fusion under agitation and homogenizing under 190 ℃ of temperature.The mixture melt that obtains is poured in the porcelain dish, and it cools off post-hardening.Every batch scale is 50g.
Table 11
Component 1 and 2 amount in the mixture of the present invention (11)
Mixture Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester [weight %] 1,1,1-three (diphenylphosphine ylmethyl) basic propane [weight %]
????11a ????100 ????0
????11b ????70 ????30
????11c ????50 ????50
????11d ????30 ????70
????11e ????0 ????100
Embodiment 12
In order to prepare according to stable polymer of the present invention (12a), will
100.00 the linear low density polyethylene (LLDPE) of part
0.05 the Hostanox O 16 of part
0.10 part calcium stearate and
0.04 the mixture of the present invention (10a) of part
It is a powder type, mixes in mixing machine, makes its homogenizing, the polymer-extruded thing pelletizing that will obtain then by extruding then under mild conditions in single screw extrusion machine (Haendle, KPS25,210 ℃, 80/min, compr.1: 3, die head 4mm).Prepare stable polymer (12b) to (12e) from mixture (10b) to (10e) similarly.
In order to study melt flow stabilization and colour stableization, these stable polymer (12a) are carried out 5 time in 240 ℃ to (12e) extrude in single screw extrusion machine (G ttfert Extrusiometer, 70/min, compr.1: 3, die head 4mm).According to ASTM 1238, condition L (190 ℃/2.16kg) melt flow index (MFI) and according to the yellowness index (YI) of DIN 6167 the 5th time by after mensuration.What obtain the results are shown in following table.
Table 12
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (10a) to the LLDPE of (10e)
Stable polymer Two (diphenylphosphine bases)-2,2-dimethylpropane [weight %] The 5th is passed through
?MFI[g/10min] ????YI
????12a ????0 ????1.35 ????10.51
????12b ????30 ????1.60 ????9.88
????12c ????50 ????1.83 ????9.13
????12d ????70 ????2.08 ????8.16
????12e ????100 ????2.19 ????8.41
Embodiment 13
Prepare stable polymer (13a) to (13e) in the mode that is similar among the embodiment 12 from mixture (10a) to (10e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 13
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (10a) to the LLDPE of (10e)
Stable polymer Two (diphenylphosphine bases)-2,2-dimethylpropane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????13a ????0 ????1.51 ???9.58
????13b ????30 ????1.87 ???7.00
????13c ????50 ????2.11 ???7.34
????13d ????70 ????2.25 ???5.69
????13e ????100 ????2.28 ???4.25
Embodiment 14
Prepare stable polymer (14a) to (14e) in the mode that is similar among the embodiment 12 from mixture (11a) to (11e), concentration is 0.04 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 14
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (11a) to the LLDPE of (11e)
Stable polymer 1,1,1-three (diphenylphosphine ylmethyl) propane [weight %] The 5th is passed through
??MFI[g/10?min] ????YI
????14a ????0 ????1.35 ??10.51
????14b ????30 ????1.65 ??6.20
????14c ????50 ????1.85 ??5.00
????14d ????70 ????1.99 ??5.41
????14e ????100 ????2.13 ??9.12
Embodiment 15
Prepare stable polymer (15a) to (15e) in the mode that is similar among the embodiment 12 from mixture (11a) to (11e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 15
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (11a) to the LLDPE of (11e)
Stable polymer 1,1,1-three (diphenylphosphine ylmethyl) propane [weight %] The 5th is passed through
MFI[g/10min] ???YI
????15a ????0 ????1.51 ??9.58
????15b ????30 ????1.96 ??5.49
????15c ????50 ????2.07 ??5.40
????15d ????70 ????2.21 ??3.67
????15e ????100 ????2.27 ??4.40
Embodiment 16
Prepare stable polymer (16a) to (16e) in the mode that is similar among the embodiment 12 from mixture (1a) to (1e), concentration is 0.04 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 16
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (1a) to the LLDPE of (1e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
MFI[g/10min] ????YI
????16a ????0 ????1.35 ????10.51
????16b ????30 ????1.71 ????7.63
????16c ????50 ????1.95 ????6.83
????16d ????70 ????1.96 ????8.64
????16e ????100 ????2.15 ????11.55
Embodiment 17
Prepare stable polymer (17a) to (17e) in the mode that is similar among the embodiment 12 from mixture (1a) to (1e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 17
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (1a) to the LLDPE of (1e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
????MFI[g/10min]
????17a ????0 ????1.51
????17b ????30 ????2.02
????17c ????50 ????2.04
????17d ????70 ????2.16
????17e ????100 ????2.30
Embodiment 18
In order to prepare according to stable polymer of the present invention (18a), will
100.00 the high density polyethylene(HDPE) (HDPE) of part
0.05 the Hostanox O 10 of part
0.10 part calcium stearate and
0.04 the mixture of the present invention (10a) of part
It is a powder type, mixes in mixing machine, makes its homogenizing, the polymer-extruded thing pelletizing that will obtain then by extruding then under mild conditions in single screw extrusion machine (Haendle, 25,210 ℃ of KPS, 80/min, compr.1: 3, die head 4mm).Prepare stable polymer (18b) to (18e) from mixture (10b) to (10e) similarly.
In order to study melt flow stabilization and colour stableization, these stable polymer (18a) are carried out 5 time in 240 ℃ to (18e) extrude in single screw extrusion machine (G ttfert Extrusiometer, 70/min, compr.1: 3, die head 3mm).According to ASTM 1238, condition L (190 ℃/2.16kg) melt flow index (MFI) and according to the yellowness index (YI) of DIN 6167 the 5th time by after mensuration.What obtain the results are shown in following table.
Table 18
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (10a) to the HDPE of (10e)
Stable polymer Two (diphenylphosphine bases)-2,2-dimethylpropane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????18a ????0 ????6.15 ????2.92
????18b ????30 ????7.00 ????1.06
????18c ????50 ????6.92 ????-0.95
????18d ????70 ????6.87 ????-1.19
????18e ????100 ????6.84 ????-1.00
Embodiment 19
Prepare stable polymer (19a) to (19e) in the mode that is similar among the embodiment 18 from mixture (10a) to (10e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 19
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (10a) to the HDPE of (10e)
Stable polymer Two (diphenylphosphine bases)-2,2-dimethylpropane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????19a ????0 ????6.46 ????2.73
????19b ????30 ????6.64 ????-1.98
????19c ????50 ????6.84 ????-1.40
????19d ????70 ????6.61 ????-1.85
????19e ????100 ????6.70 ????-1.08
Embodiment 20
Prepare stable polymer (20a) to (20e) in the mode that is similar among the embodiment 18 from mixture (11a) to (11e), concentration is 0.04 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 20
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (11a) to the HDPE of (11e)
Stable polymer 1,1,1-three (diphenylphosphine ylmethyl) propane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????20a ????0 ????6.15 ???2.92
????20b ????30 ????6.89 ???2.67
????20c ????50 ????6.84 ???2.10
????20d ????70 ????6.61 ???-0.48
????20e ????100 ????6.82 ???-1.36
Embodiment 21
Prepare stable polymer (21a) to (21e) in the mode that is similar among the embodiment 18 from mixture (11a) to (11e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 21
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (11a) to the HDPE of (11e)
Stable polymer 1,1,1-three (diphenylphosphine ylmethyl) propane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????21a ????0 ????6.46 ????2.73
????21b ????30 ????6.90 ????1.44
????21c ????50 ????6.87 ????0.19
????21d ????70 ????6.92 ????-0.48
????21e ????100 ????6.84 ????-0.25
Embodiment 22
Prepare stable polymer (22a) to (22e) in the mode that is similar among the embodiment 18 from mixture (1a) to (1e), concentration is 0.04 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 22
Use melt flow stabilization and the colour stable result of 0.04 part of mixture (1a) to the HDPE of (1e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
??MFI[g/10min] ?????YI
????22a ????0 ????6.15 ????2.92
????22b ????30 ????6.89 ????0.96
????22c ????50 ????6.74 ????1.69
????22d ????70 ????7.00 ????-0.92
????22e ????100 ????6.59 ????0.04
Embodiment 23
Prepare stable polymer (23a) to (23e) in the mode that is similar among the embodiment 18 from mixture (1a) to (1e), concentration is 0.07 part of mixture of the present invention, and tests accordingly.What obtain the results are shown in following table.
Table 23
Use melt flow stabilization and the colour stable result of 0.07 part of mixture (1a) to the HDPE of (1e)
Stable polymer Triphenylphosphine alkane [weight %] The 5th is passed through
??MFI[g/10min] ????YI
????23a ????0 ????6.46 ????2.73
????23b ????30 ????6.88 ????-0.35
????23c ????50 ????6.91 ????-0.64
????23d ????70 ????6.86 ????-1.26
????23e ????100 ????6.85 ????-0.04
Clearly illustrate as the result of these embodiment, these mixtures of the present invention (1) to (3) and (10) and (11) have obvious synergistic with used as stabilizers, (MFI and YI are respectively to concentration of component in the mixture) more can illustrate this point if the result is presented in diagrammatic form.In all cases, the curve of measuring performance (MFI value or YI value) is positioned at a side of better stabilization, and therefore be lower than (MFI of PP and all YI) or be higher than straight line that is connected independent component of (MFI of LLDPE and HDPE) theoretical anticipation, promptly the performance beguine of mixture according to linear interpolation expect good.

Claims (5)

1. mixture, it comprises
A) at least a compound (being called component 1 hereinafter) that is selected from general formula (I) to (XV) compound
Figure A0181271000021
Figure A0181271000022
Figure A0181271000041
Figure A0181271000051
With
B) at least a compound (being called component 2 hereinafter) that is selected from general formula (XVI) to (XIX) compound
Figure A0181271000053
Figure A0181271000054
Figure A0181271000055
Wherein, independently of each other, each group
R 1Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 2Be H, C 1-C 24Alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 3Be the group of n-valency, its type is C 1-C 30-alkylidene group (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 1-C 30-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 12-cycloalkylidene or C 6-C 24-arylidene is (if suitably by C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18Alkoxyl group replaces);
R 4Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 5Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
R 6Be C 1-C 24-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 30-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 30-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 12-cycloalkyl or C 1-C 18-alkoxyl group replaces);
A is direct keyed jointing, C 1-C 30-alkylidene (if suitably also comprising heteroatoms N, O, P, S),＞NH,＞NR 1,-S-,＞S (O),＞S (O) 2,-O-;
D is the group of q-valency, and its type is C 1-C 30-alkylidene group (straight chain, side chain is if suitably also comprise heteroatoms N, O, P, S), C 1-C 30-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 12-cycloalkylidene (if suitably also comprising heteroatoms N, O, P, S) or C 6-C 24-arylidene is (if suitably by C 1-C 18-alkyl (straight or branched), C 5-C 12Cycloalkyl or C 1-C 18Alkoxyl group replaces) ,-O-,-S-;
X is Cl, Br, F, OH (tautomeric form＞P (O) H that comprises generation);
K is 0 to 4;
N is 1 to 4;
M is 0 to 5;
P is 0 or 1;
Q is 1 to 5;
R is 3 to 6, the group P-R in its formula of (XIX) 6Be the structure branch of phosphorus heterocycle, represent by the * on the key that even goes out from P.
2. the mixture of claim 1, wherein, independently of each other
R 1' be C 6-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 2-C 24-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12Alkoxyl group replaces);
R 2' be H, C 1-C 12-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 18-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 3' be the group of n-valency, its type is C 1-C 14-alkylidene group (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 1-C 18-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 8-cycloalkylidene or C 6-C 24-arylidene is (if suitably by C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 4' be C 1-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 24-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 5' be C 8-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 18-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 6' be C 5-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 5-C 12-cycloalkyl (if suitably also comprising heteroatoms N, O, P, S), C 1-C 18-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
A ' is direct keyed jointing, C 1-C 18-alkylidene (if suitably also comprising heteroatoms N, O, P, S),＞NH ,-S-,-O-;
D ' is the group of q '-valency, and its type is C 1-C 24-alkylidene group (straight chain, side chain is if suitably also comprise heteroatoms N, O, P, S), C 1-C 24-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 8-cycloalkylidene (if suitably also comprising heteroatoms N, O, P, S) or C 6-C 24-arylidene is (if suitably also by C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
X ' is F or OH (tautomeric form＞P (O) H that comprises generation);
K ' is 0 to 3;
N ' is 1 to 4;
M ' is 0 to 3;
P ' is 0 or 1;
Q ' is 1 to 4;
R ' is 4 or 5, the group P-R in its formula of (XIX) 6Be the structure branch of phosphorus heterocycle, represent by the * on the key that even goes out from P.
3. the mixture of claim 1, wherein, independently of each other
R 1" be C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
R 2" be C 1-C 8-alkyl (straight or branched), C 5-C 8-cycloalkyl, C 1-C 18-alkylaryl, C 6-C 12-aryl or heteroaryl, C 6-C 12-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 3" be the group of n-valency, its type is C 1-C 12-alkylidene group (straight or branched is if suitably also comprise heteroatoms N or P), C 1-C 12-alkylidene (if suitably also comprising heteroatoms N or P), C 6-C 8-cycloalkylidene or C 6-C 12Arylidene is (if suitably also by C 1-C 12-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 4" be C 1-C 8-alkyl (straight or branched), C 5-C 8-cycloalkyl, C 1-C 18-alkylaryl, C 6-C 12-aryl or heteroaryl, C 6-C 12-aryl or heteroaryl are (by group C 1-C 12-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 5" be C 12-C 18-alkyl (straight or branched is if suitably also comprise heteroatoms N, O, P, S), C 6-C 8-cycloalkyl, C 1-C 12-alkylaryl, C 6-C 18-aryl or heteroaryl, C 6-C 18-aryl or heteroaryl are (by group C 1-C 8-alkyl (straight or branched), C 6-C 8-cycloalkyl or C 1-C 8-alkoxyl group replaces);
R 6" be C 5-C 12-alkyl (straight or branched), C 5-C 8-cycloalkyl, C 1-C 12-alkylaryl, C 6-C 24-aryl or heteroaryl, C 6-C 24-aryl or heteroaryl are (by group C 1-C 18-alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
A " be direct keyed jointing, C 1-C 18-alkylidene (if suitably also comprising heteroatoms N, O, P, S),＞NH ,-S-,-O-;
D " be q "-group of valency, its type is C 1-C 24-alkylidene group (straight chain, side chain is if suitably also comprise heteroatoms N, O, P, S), C 1-C 24-alkylidene (if suitably also comprising heteroatoms N, O, P, S), C 5-C 8-cycloalkylidene (if suitably also comprising heteroatoms N, O, P, S) or C 6-C 24-arylidene is (if suitably also by C 1-C 18Alkyl (straight or branched), C 5-C 8-cycloalkyl or C 1-C 12-alkoxyl group replaces);
X " be F or OH (tautomeric form＞P (O) H that comprises generation);
K " be 0 to 3;
N " be 1 to 4;
M " be 0 to 3;
P " be 0 or 1;
Q " be 1 to 4;
R " be 4 or 5, the group P-R in its formula of (XIX) 6Be the structure branch of phosphorus heterocycle, represent by the * on the key that even goes out from P.
4. the mixture of claim 1, wherein the weight ratio of component 1 is that the weight ratio of component 2 in 1 to 99 weight %, preferred 5 to 95 weight %, preferred especially 10 to 90 weight % and the mixture is 99 to 1 weight %, preferred 95 to 5 weight %, preferred especially 90 to 10 weight % in the mixture.
5. the method that is used for stabilization of polymer aspect thermooxidative degradation, it comprises adding and in conjunction with being the mixture according to claim 1 of the amount of 0.001 to 5 weight %, preferred 0.005 to 3 weight %, preferred especially 0.01 to 2 weight % based on the polymkeric substance that is stabilized, this mixture is solid or liquid/fusion form, solution or solid master batch form.
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